I would like to know if it’s possible and if so, how does one make a payment using available funds?
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If this is true then why is it telling me that I have until 11:59pm to make my payment?
It's just some catchall boilerplate text on the page.
If you have available funds equal to or more than your plan cost then it'll take from there first.
If you have autopay set up and less than the plan cost then it'll drain you available funds and take what else it needs from the autopay.